EP0998851B1 - Antibacterial and antifungal resin composition - Google Patents
Antibacterial and antifungal resin composition Download PDFInfo
- Publication number
- EP0998851B1 EP0998851B1 EP99120991A EP99120991A EP0998851B1 EP 0998851 B1 EP0998851 B1 EP 0998851B1 EP 99120991 A EP99120991 A EP 99120991A EP 99120991 A EP99120991 A EP 99120991A EP 0998851 B1 EP0998851 B1 EP 0998851B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bis
- bromide
- group
- carbon atoms
- carbamoyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 56
- 239000011342 resin composition Substances 0.000 title claims description 29
- 230000000843 anti-fungal effect Effects 0.000 title description 25
- 229940121375 antifungal agent Drugs 0.000 title description 19
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000002781 deodorant agent Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 210000002700 urine Anatomy 0.000 claims description 11
- PNXWPUCNFMVBBK-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+]1=CC=CC=C1 PNXWPUCNFMVBBK-UHFFFAOYSA-M 0.000 claims description 6
- LNKPCMOUFKLBCM-UHFFFAOYSA-M 1-octylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCC[N+]1=CC=CC=C1 LNKPCMOUFKLBCM-UHFFFAOYSA-M 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- WDBZIOOWEOBTPZ-UHFFFAOYSA-N 1-decylpyridin-1-ium-4-carboxamide;acetate Chemical compound CC([O-])=O.CCCCCCCCCC[N+]1=CC=C(C(N)=O)C=C1 WDBZIOOWEOBTPZ-UHFFFAOYSA-N 0.000 claims description 3
- OQXBPCPZNLQMTK-UHFFFAOYSA-N 1-decylpyridin-1-ium-4-carboxamide;bromide Chemical compound [Br-].CCCCCCCCCC[N+]1=CC=C(C(N)=O)C=C1 OQXBPCPZNLQMTK-UHFFFAOYSA-N 0.000 claims description 3
- SPFVNQBOHYXSMM-UHFFFAOYSA-M 1-decylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCC[N+]1=CC=CC=C1 SPFVNQBOHYXSMM-UHFFFAOYSA-M 0.000 claims description 3
- 125000004450 alkenylene group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000006839 xylylene group Chemical group 0.000 claims description 3
- HJUPHPDWOUZDKH-UHFFFAOYSA-M 1-decylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+]1=CC=CC=C1 HJUPHPDWOUZDKH-UHFFFAOYSA-M 0.000 claims description 2
- IGQNITWOOQMZGG-UHFFFAOYSA-M 1-decylpyridin-1-ium;iodide Chemical compound [I-].CCCCCCCCCC[N+]1=CC=CC=C1 IGQNITWOOQMZGG-UHFFFAOYSA-M 0.000 claims description 2
- ZTOVMCASWOXRHW-UHFFFAOYSA-N 1-hexadecylpyridin-1-ium-4-carboxamide;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=C(C(N)=O)C=C1 ZTOVMCASWOXRHW-UHFFFAOYSA-N 0.000 claims description 2
- JDASKPRUFDKACZ-UHFFFAOYSA-M 1-octadecylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 JDASKPRUFDKACZ-UHFFFAOYSA-M 0.000 claims description 2
- TTXLFUJSPVEFDO-UHFFFAOYSA-M 1-octadecylpyridin-1-ium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 TTXLFUJSPVEFDO-UHFFFAOYSA-M 0.000 claims description 2
- AAPKSSLJOXMRHK-UHFFFAOYSA-N 1-octylpyridin-1-ium-4-carboxamide;bromide Chemical compound [Br-].CCCCCCCC[N+]1=CC=C(C(N)=O)C=C1 AAPKSSLJOXMRHK-UHFFFAOYSA-N 0.000 claims description 2
- XDCILYQINRVJBM-UHFFFAOYSA-M 1-octylpyridin-1-ium;iodide Chemical compound [I-].CCCCCCCC[N+]1=CC=CC=C1 XDCILYQINRVJBM-UHFFFAOYSA-M 0.000 claims description 2
- PDKQYPVFZJXIBB-UHFFFAOYSA-N 1-tetradecylpyridin-1-ium-3-carboxamide;bromide Chemical compound [Br-].CCCCCCCCCCCCCC[N+]1=CC=CC(C(N)=O)=C1 PDKQYPVFZJXIBB-UHFFFAOYSA-N 0.000 claims description 2
- HJNAJKBRYDFICV-UHFFFAOYSA-M 1-tetradecylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCC[N+]1=CC=CC=C1 HJNAJKBRYDFICV-UHFFFAOYSA-M 0.000 claims description 2
- DKHPZKVRYNAIKN-UHFFFAOYSA-M CC([O-])=O.CCCCCCCCCC[N+]1=CC=CC=C1 Chemical compound CC([O-])=O.CCCCCCCCCC[N+]1=CC=CC=C1 DKHPZKVRYNAIKN-UHFFFAOYSA-M 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000539 dimer Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 20
- 239000000835 fiber Substances 0.000 description 19
- 241000894006 Bacteria Species 0.000 description 18
- 229940088710 antibiotic agent Drugs 0.000 description 16
- 241000233866 Fungi Species 0.000 description 14
- 239000002952 polymeric resin Substances 0.000 description 14
- 229920003002 synthetic resin Polymers 0.000 description 14
- -1 2-ethylhexyl Chemical group 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 241000191967 Staphylococcus aureus Species 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229960000686 benzalkonium chloride Drugs 0.000 description 6
- XIWFQDBQMCDYJT-UHFFFAOYSA-M benzyl-dimethyl-tridecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XIWFQDBQMCDYJT-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
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- 230000036325 urinary excretion Effects 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 241001646716 Escherichia coli K-12 Species 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 4
- 241000228245 Aspergillus niger Species 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 241000588770 Proteus mirabilis Species 0.000 description 3
- 108010046334 Urease Proteins 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- 239000006285 cell suspension Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000029142 excretion Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- 229940123208 Biguanide Drugs 0.000 description 2
- 241001515917 Chaetomium globosum Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 241000192125 Firmicutes Species 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 241000588747 Klebsiella pneumoniae Species 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 241001136494 Talaromyces funiculosus Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 150000004283 biguanides Chemical class 0.000 description 2
- 238000002815 broth microdilution Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
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- 150000003673 urethanes Chemical class 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001465318 Aspergillus terreus Species 0.000 description 1
- 241000223678 Aureobasidium pullulans Species 0.000 description 1
- 241000193755 Bacillus cereus Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001149955 Cladosporium cladosporioides Species 0.000 description 1
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- 206010011409 Cross infection Diseases 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 206010052804 Drug tolerance Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
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- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
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- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
- A61L2300/208—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
Definitions
- This invention relates to antibacterial and antifungal resin compositions which can be used in a wide range of applications requiring antibacterial and antifungal properties from the viewpoint of health and hygiene, such as disposable diapers and urine disposal articles for pets.
- Moldings formed of polymeric resins essentially have relatively good antifungal properties, and are hence being used as surfacing materials for various building materials, household goods, insoles of shoes, and the like.
- various antifungal agents such as those of the arsenic, imidazole and thiazole types, in the polymeric resins (see, for example, Japanese Patent Laid-Open No. 259054/'89 and 207090/'95).
- antibacterials incorporated in polymeric resins include Quaternary ammonium salts and biguanides (see, for example, Japanese Patent Laid-Open No. 259054/'89 and 324070/ '97). These antibacterials are effective against bacteria, but have no antifungal effect. In order to obtain polymeric resin products having antibacterial and antifungal properties, antifungal agents must be used in combination with them.
- Japanese Patent JP 10 095773A discloses bis quaternary ammonium salts having an efficient sterilisation effect and shows a wide range of antibacterial spectrum.
- disposable diapers whether for babies or for adults, are being increasingly used in place of cloth diapers, because of their excellent absorption capacity and convenience in handling. It is expected that, in future, demand for dispos able diapers will continue to expand with the spread of their use.
- disposable diapers consist of a water-pervious facing sheet, a water-impervious backing sheet, and a water-absorbing layer interposed between these sheets.
- the water-absorbing layer there is used pulp, a highly water-absorbing polymer or the like.
- An object of the present invention is to provide a resin composition which exhibits not only an excellent antibacterial effect on both gram-positive and gram-negative bacteria, but also an excellent antifungal effect, and can hence been used in a wide range of applications requiring antibacterial and antifungal properties from the viewpoint of health and hygiene.
- Another specific object of the present invention is to provide a water-absorbing deodorant resin composition which exhibits an excellent antibacterial effect on bacteria producing substances responsible for an offensive odor from urea and other compounds present in urine, particularly skin flora bacteria capable of producing urease, also shows a broad antibacterial spectrum against gram-positive and gram-negative bacteria, and is markedly effective in preventing the generation of an offensive odor arising from urinary excretion.
- a disposable diaper characterized by using, as a water-absorbing material a deodorant water-absorbing resin composition comprising a highly water-absorbing resin and antibacterial bis-pyridinum compound of the general formula wherein the two R 1 may be the same or different and each represent an alkyl group of 1 to 18 carbon atoms or an alkenyl group of 3 to 18 carbon atoms; the two R 2 may be the same or different, and each represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group of 1 to 6 carbon atoms, or an alkoxy group of 1 to 3 carbon atoms; R 3 represents an alkylene group of 2 to 18 carbon atoms, an alkenylene group of 3 to 18 carbon atoms, or a phenylene or xylylene group which may optionally be substituted by an alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, or an al
- antibacterial and antifungal resin compositions will be more specifically described hereinbelow.
- alkyl group denotes a straight-chain or branched alkyl group, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl and octadecyl, etc.
- the alkyl groups represented by R 1 are preferably ones having 8 or more carbon atoms.
- alkenyl group denotes a straight-chain or branched alkenyl group, and examples thereof include allyl, methallyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl and octadecenyl, etc.
- alkoxy group denotes an alkyloxy group in which the alkyl moiety has the above-described meaning, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy.
- alkylene group preferably denotes a group of the formula -(-CH 2 -) n -.
- n is preferably in the range of 2 to 18 and more preferably 3 to 8.
- alkoxycarbonyl group denotes an alkyloxycarbonyl group in which the alkyl moiety has the above-described meaning, and examples thereof include methoxycarbonyl and ethoxycarbonyl.
- halogen atom comprehends fluorine, chlorine, bromine and iodine.
- anion comprehends inorganic anions such as halogen ions (e.g., Cl - , Br - and I - ) and nitrate ion (NO 3 - ); and organic acid anions such as acetate ion (CH 3 COO - ) and propionate ion (C 2 H 5 COO - ).
- halogen ions e.g., Cl - , Br - and I -
- NO 3 - nitrate ion
- organic acid anions such as acetate ion (CH 3 COO - ) and propionate ion (C 2 H 5 COO - ).
- a preferred group of compounds are those of formula (I) in which the two R 1 may be the same or different, and each represent an alkyl group of 8 to 18 carbon atoms; the two R 2 may be the same or different, and each represent a hydrogen atom or a chlorine atom; R 3 represents an alkylene group of 3 to 8 carbon atoms, a phenylene group or a xylylene group; Y 1 represents -NHCO-, -CONH-, -COO- or -S-; Y 2 represents -CONH-, -NHCO-, -OOC- or -S-; and X represents a halogen ion or an acetate ion.
- any desired polymeric resin may be freely chosen according to the intended use of the resin composition of the present invention, and the like.
- usable resins include vinyl chloride polymers. urethane polymers.
- acrylate polymers olefin polymers, ethylene polymer, propylene polymer, polyamides, ethylene-vinyl acetate copolymers, vinylidene chloride polymer, styrene polymers, ester polymers, nylons, cellulose derivatives, polycarbonates, fluorinated resins, silicone resins, vinyl alcohol polymers, vinyl ester polymers, compounds and natural rubber. These resins may be used alone or as a blend of two or more.
- the antibacterial and antifungal resin compositions used in the present invention may be prepared by dispersing an antibacterial compound of the above formula (I) in a polymeric resin as described above. More specifically, the resin compositions may be obtained, for example, by adding the compound of formula (I) in the polymeric resin and melt-kneading this mixture, by adding the compound of formula (I) or a solution thereof to a solution of the polymeric resin and agitating this mixture, or by polymerizing a monomer and monomers with the compound of formula (I) or a solution thereof. Alternatively, the compound of formula (I) may be chemically bonded to the polymeric resin.
- the amount of the compound of formula (I) incorporated in the polymeric resin is not strictly limited, but may vary according to the type of the resin used, the type of the compound of formula (I) used, the use of the resulting resin composition, and the like. However, the amount is generally in the range of 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 2 part by weight, per 100 parts by weight of the polymeric resin.
- plasticizers may optionally be incorporated in the resin compositions of the present invention.
- fillers i.e., dyes and pigments
- colorants i.e., dyes and pigments
- ultraviolet-radiation absorbers may optionally be incorporated in the resin compositions of the present invention.
- the resin compositions used in the present invention may be processed into various forms according to their intended use and the like.
- the resin compositions of the present invention may be formed into films, sheets, plates, fibers or three-dimensional articles, and may be used, for concrete example, as interior decorative materials (e.g., wallpaper), as flooring materials (e.g., tiles), and in home electrical appliances (e.g., refrigerators, washing machines and dryers).
- the resin compositions used in the present invention may also be formed into antibacterial paints by using them as vehicles. This can be done, for example, by dissolving or dispersing the resin composition in a paint solvent and adding suitable paint additives (e.g.; pigments and crosslinking agents) to the resulting solution or dispersion.
- suitable paint additives e.g.; pigments and crosslinking agents
- the resin compositions of the present invention may be applied to . fiber products and paper products in the form of organic solvents or aqueous emulsions.
- the applications include, for example, padding, dipping, spraying, printing, coating, gravure coating and foam laminating.
- the polymeric resins suitable for use in such treatment of fiber products and paper products include, for example, starch, carboxymethylcellulose, urethane resins, acrylate resins, epoxy resins, vinyl chloride resins, vinyl acetate resins, fluorinated resins, silicone resins, polyamide resins, polyester resins, glyoxal resin, polyvinylidene fluoride resins, styrene resins, butadiene resins, acrylonitrile-butadiene resins, acrylate resins, ethylene-vinyl acetate resins, acrylate-ethylene-vinyl acetate resins and ethylene-vinyl chloride resins.
- the fiber products and paper products which can be treated with the resin compositions of the present invention to impart antibacterial and antifungal processing thereto.
- They include, for example, various kinds of products formed from synthetic fibers such as polyester fibers, polyamide fibers, acrylic fibers, polyolefin fibers and polyvinyl chloride fibers; semisynthetic fibers such as acetates; regenerated fibers such as rayon; natural fibers such as cotton, flax, wool, silk and pulp; and composite materials obtained from these fibers by mix spinning, mixed weaving, combined twisting, combined weaving, combined knitting or fiber blending. More specifically, they include fibers such as filaments and staple, threads such as filament yarn and spun yarn; textile materials such as woven fabrics, knitted fabrics and nonwoven fabrics; paper-like materials formed of fibers; and fiber products and paper products made of these materials.
- the fiber and paper products treated with said resin compositions include, for example, linen products for use in hospitals, sanitary products, bedclothes, socks, supporters, carpets, toiletry goods, kitchen utensils, toys, filters for electrical appliances, wet tissue, helmets and wallpaper, etc.
- a highly water-absorbing resin may be used as the starting resin. This makes it possible to provide a water-absorbing resin composition which has excellent deodorant properties and can hence be used in sanitary products including, in particular, disposable diapers, and urine disposal articles for pets.
- the highly water-absorbing resin included in this water-absorbing resin composition there may be used any of the highly water-absorbing resins commonly used in disposable diapers and sanitary products (e.g., sanitary napkins).
- examples thereof include starch-based water-absorbing resins such as soluble starch-acrylonitrile graft copolymer and starch-acrylic acid graft copolymer; cellulose-based water-absorbing resins such as crosslinked graft cellulose and crosslinked carboxymethylcellulose; and synthetic polymer-based water-absorbing resins such as partially crosslinked polyoxyethylene, partially crosslinked acrylate or methacrylate polymers, partially crosslinked acrylate or methacrylate copolymers, and vinyl alcohol-acrylate copolymer. It is generally preferable that these resins have the ability to absorb several hundred to several thousand times as much water as their own weight. The resins may be used alone or in combination of two or more.
- An antibacterial compound of the above formula (I) may be incorporated in such a highly water-absorbing resin according to any of the per se known methods. This may be done, for example, (1) by allowing a powder of the highly water-absorbing resin to absorb an aqueous solution containing an appropriate amount of the compound of formula (I), followed drying; (2) by adding an appropriate amount of the compound of formula (I), in the form of a powder or a solution, to the highly water-absorbing resin at any stage of the preparation of the resin; or (3) by mixing a powder of the highly water-absorbing resin with an appropriate amount of the compound of formula (I) in powder form.
- the above-described methods (1) and (2) are preferred for the purpose of highly dispersing the compound of formula (I).
- the water-absorbing resin composition prepared in the above-described manner may be processed into various forms. No particular limitation is placed on such forms.
- the water-absorbing resin composition may be formed into powders, granules, sheets or fibers according to the intended use of the final product, and the like.
- it may be formed into water-absorbing fibers of two-layer structure in which an acrylic fiber is incorporated as the core (e.g., "Lanseal F” manufactured by Toyobo Co., Ltd.).
- the amount of the antibacterial compound of formula (I) incorporated in the highly water-absorbing resin is not strictly limited, but may vary according to the type of the antibacterial compound used, and the like. However, the antibacterial compound of formula (I) is generally used in an amount of 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 2 parts by weight, per 100 parts by weight of the resin.
- the highly water-absorbing resin having the antibacterial compound of formula (I) incorporated therein as described above is used as a water-absorbing resin for sanitary products and, in particular, disposable diapers, it becomes possible to provide hygienic disposable diapers which can effectively prevent the generation of an offensive odor arising from urinary excretion.
- the highly water-absorbing resin conventionally used in the water-absorbing layer may be replaced by the water-absorbing resin composition of the present invention.
- the disposable diapers thus obtained can inhibit the growth of bacteria decomposing urea and other compounds present in urine to produce ammonia, methylamine, etc., and thereby prevent the generation of an offensive odor due to the decomposition of urea and other compounds. Moreover, they can also inhibit the growth of various microorganisms such as Escherichia coli and Candida species, and can hence be expected to improve unhygienic conditions attributable to such various microorganisms.
- litter comprising a highly water-absorbing resin and, moreover, such litter having added thereto antibacterials and a deodorant have recently come into the market. In the present circumstance, however, they are not satisfactorily effective in preventing the generation of an offensive odor. Although some patience or habituation may make the keeper insensitive to the odor of pets because they are practically members of the family, occasional visitors tend to suffer from an unpleasant odor.
- the deodorant water-absorbing resin compositions of the present invention can more effectively prevent the generation of an offensive odor due to the decomposition of urine, and the growth of various microorganisms, than other antibacterials. Accordingly, the deodorant water-absorbing resin compositions used in the present invention can contribute greatly to the prevention of an offensive odor arising from pets, the maintenance of a hygienic environment, and a decrease in the freq offensive odor uency of exchange of urine disposal articles for pets.
- Antibacterial urethanes were obtained by adding 1 phr of N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) (hereinafter referred to as "Dimer 38"), 4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide) (hereinafter referred to as "Dimer 136) or inorganic antibacterials containing silver to an ether type urethane and an ester type urethane.
- the antibacterial urethanes thus obtained were subjected to antibacterial tests according to a film covering method.
- each specimen (5 cm x 5 cm) was placed in a sterile petri dish, and the test surface was inoculated with 0.5 ml of a cell suspension and was covered with a sterile polyethylene film.
- the petri dish was covered and allowed to stand at 37°C for 24 hours. Thereafter, using SCDLP medium (9.5 ml), the bacterial cells attached to the specimen and the coating film were thoroughly washed out into the another sterile petri dish.
- the viable cell number present in 1 ml of the washings was counted according to the agar dilution method.
- Three specimens were tested for each sample, and the viable cell count was calculated as the average of the three specimens.
- two strains of bacteria Staphylococcus aureus IFO 12732 and Escherichia coli K12 W3110, were used. The results thus obtained are shown in Table 1.
- Antifungal vinyl chloride polymer sheets were formed from polyvinyl chloride having 0.5% of Dimer 38, Dimer 136 or inorganic antibacterials containing zinc. Fungus resistance of the antifungal sheets were assessed by the modified method of JIS Z 2911 (Japanese Industrial Standards Committee, 1992). Concretely, a specimen (4 cm x 4 cm) of each sheet was placed in a petri dish containing a mineral nutrient agar, and 0.5 ml of the mixed spore suspension was uniformly inoculated on the agar and the specimen. The petri dish was covered, incubated at 28°C for 9 weeks, and observed for the growth of fungi at intervals of one week.
- Antibacterial SAPs Water-absorbing resins containing antibacterials
- AQUAPEARL ZS45 a highly water-absorbing resin powder
- the antibacterials comprised (Dimer 38).
- Dimer 38A N,N'-hexamethylene-bis(4-carbamoyl-1-decylpyridinium acetate)
- benzalkonium chloride a highly water-absorbing resin powder
- Dimer 38A N,N'-hexamethylene-bis(4-carbamoyl-1-decylpyridinium acetate
- Antibacterial SAPs containing Dimer 38, Dimer 38A or benzalkonium chloride were prepared in the same method as in Example 3.
- One gram of each of the antibacterial SAPs thus obtained was placed in a test tube, to which 10 ml of human urine and 1 ml of the cell suspension (about 10 6 cells/ml) of Proteus mirabilis IFO 3849 were added.
- the test tube was incubated at 37°C. After 6 and 24 hours, the concentration of ammonia in the test tube was measured with a smell sensor (Portable Smell Sensor XP-329; manufactured by Shin Cosmos Electric Co., Ltd.). The results are shown in Table 4.
- the minimum inhibitory concentrations (MICs), namely the bacteriostasis powers, of Dimer 38 and Dimer 136 were determined and compared with that of benzalkonium chloride.
- Their minimum inhibitory concentrations (MICs) of antimicrobials were measured by the broth dilution method. Concretely, using nutrient broth, the cell concentration in stationary phase was adjusted to 10 6 cells/ml, and aliquots thereof were mixed with serially diluted solutions of each antibacterials. These mixtures were incubated at 37°C for 24 hours and the MICs were determined by visual inspection. In these tests, 8 strains of gram-negative bacteria and 4 strains of gram-positive bacteria were used. The results are shown in Table 5.
- Dimer 38 and Dimer 136 exhibit equally strong bacteriostatic efficiency against all of the 8 strains of gram-negative bacteria including Escherichia coli and the 4 strains of gram-positive bacteria including MRSA, and hence have wide bacteriostatic spectra over that of benzalkonium chloride.
- the bacteriostasis against Proteus mirabilis IFO 3849 that is a bacterium producing an enzyme (urease) capable of degrading urea and other compounds to ammonia, methylamine, etc.
- the bacteriostasis of Dimer 38 is four times and that of Dimer 136 is ten times stronger, as compared with that of benzalkonium chloride.
- MICs The minimum inhibitory concentrations (MICs), namely the antifungal efficiency, of Dimer 38 and Dimer 136 were determined and compared with that of 2-(4-thiazolyl)benzimidazole (hereinafter referred to as "TBZ").
- TTZ 2-(4-thiazolyl)benzimidazole
- MICs were measured by the broth dilution method. Concretely, using sterilized water containing a humectant, spore suspensions were prepared from preincubated fungi, and aliquots thereof were mixed with serially diluted solutions of each antibacterial or antifungal agent. These mixtures were incubated at 27°C for 1 week and the MICs were determined by visual inspection. In these antifungal tests, 10 strains of fungi were used. The results thus obtained are shown in Table 6.
- the antibacterial and antifungal resin compositions used in the present invention each comprise a polymeric resin containing an antibacterial bis-pyridinum compound which not only inhibits the growth of bacteria and shows a wide antibacterial spectrum than usual Quaternary ammonium salt compounds, but also has an antifungal effect on fungi. Consequently, they can be used in a wide range of applications requiring antibacterial and antifungal properties from the viewpoint of health and hygiene, and can be expected to improve unhygienic conditions attributable to bacteria and fungi.
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- Pest Control & Pesticides (AREA)
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Description
- This invention relates to antibacterial and antifungal resin compositions which can be used in a wide range of applications requiring antibacterial and antifungal properties from the viewpoint of health and hygiene, such as disposable diapers and urine disposal articles for pets.
- Moldings formed of polymeric resins essentially have relatively good antifungal properties, and are hence being used as surfacing materials for various building materials, household goods, insoles of shoes, and the like. In order to further improve their antifungal properties, it has been common practice to incorporate various antifungal agents, such as those of the arsenic, imidazole and thiazole types, in the polymeric resins (see, for example, Japanese Patent Laid-Open No. 259054/'89 and 207090/'95).
- However, as a result of the recently diversified use of resin products, it has become insufficient to inhibit the growth of fungi alone, and moreover there is a growing demand for products also having sufficient resistance to various kinds of bacteria such as Staphylococcus aureus and Escherichia coli. For example, fibrous materials capable of inhibiting the growth of methicillin-resistant Staphylococcus aureus (MRSA) which is posing a serious problem with hospital infection. Moreover, domestic appliances (e.g., refrigerators, washing machines and dish dryers) using plastic components having incorporated therein antibacterials for inhibiting the propagation of Escherichia coli are being put to practical use.
- Examples of antibacterials incorporated in polymeric resins include Quaternary ammonium salts and biguanides (see, for example, Japanese Patent Laid-Open No. 259054/'89 and 324070/ '97). These antibacterials are effective against bacteria, but have no antifungal effect. In order to obtain polymeric resin products having antibacterial and antifungal properties, antifungal agents must be used in combination with them.
- Japanese Patent JP 10 095773A (INUI/KK) discloses bis quaternary ammonium salts having an efficient sterilisation effect and shows a wide range of antibacterial spectrum.
- Meanwhile, in recent years, disposable diapers, whether for babies or for adults, are being increasingly used in place of cloth diapers, because of their excellent absorption capacity and convenience in handling. It is expected that, in future, demand for dispos able diapers will continue to expand with the spread of their use. Generally, disposable diapers consist of a water-pervious facing sheet, a water-impervious backing sheet, and a water-absorbing layer interposed between these sheets. For the water-absorbing layer, there is used pulp, a highly water-absorbing polymer or the like.
- Conventionally, three requirements concerning leakproofness of excretion, skin care and ease of use have been imposed on disposable diapers. Although all disposable diapers now appearing on the market meet these requirements almost satisfactorily, the existing state of the art is such that none of them have a sufficient deodorant function in eliminating the odor of urinary excretion. Generally, the odor of urinary excretion from babies is not very strong. However, adults, particularly those requiring diapers, are in a morbid state and are undergoing drug administration in many cases. Moreover, they are frequently in an unhygienic condition owing to inadequate care. For these reasons, their urinary excretion tends to emit an offensive odor. Accordingly, there is an increasing need for disposable diapers having excellent deodorant properties.
- As to the cause for the generation of an offensive odor, it is believed that, by urea-hydrolyzing enzymes and other enzymes produced by skin flora bacteria and the like, urea and other compounds present in urine are decomposed to ammonia, methylamine and like compounds which are responsible for an offensive odor. Accordingly, in order to prevent an offensive odor arising from urinary excretion in the use of a disposable diaper, it is necessary to prevent the propagation of bacteria in the water-absorbing layer of the diaper. In order to solve this problem by adding antibacterials to the water-absorbing organic polymer, there have been proposed, for example, a method using Quaternary ammonium salts and/or biguanides (see Japanese Patent Publication No. 17058 /'92) and a method using a Quaternary ammonium salt with silyl group (see Japanese Patent Laid-Open No. 245954/'94).
- However, since these antibacterials are scarcely effective against bacteria producing an enzyme (urease) capable of degrading urea and other compounds present in urea to ammonia, methylamine and the like, a satisfactory deodorant effect is not always contributed.
- An object of the present invention is to provide a resin composition which exhibits not only an excellent antibacterial effect on both gram-positive and gram-negative bacteria, but also an excellent antifungal effect, and can hence been used in a wide range of applications requiring antibacterial and antifungal properties from the viewpoint of health and hygiene.
- Another specific object of the present invention is to provide a water-absorbing deodorant resin composition which exhibits an excellent antibacterial effect on bacteria producing substances responsible for an offensive odor from urea and other compounds present in urine, particularly skin flora bacteria capable of producing urease, also shows a broad antibacterial spectrum against gram-positive and gram-negative bacteria, and is markedly effective in preventing the generation of an offensive odor arising from urinary excretion.
- Other objects and advantages of the present invention will become apparent from the following detailed description.
- According to the present invention, there is provided a disposable diaper characterized by using, as a water-absorbing material a deodorant water-absorbing resin composition comprising a highly water-absorbing resin and antibacterial bis-pyridinum compound of the general formula wherein the two R1 may be the same or different and each represent an alkyl group of 1 to 18 carbon atoms or an alkenyl group of 3 to 18 carbon atoms; the two R2 may be the same or different, and each represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group of 1 to 6 carbon atoms, or an alkoxy group of 1 to 3 carbon atoms; R3 represents an alkylene group of 2 to 18 carbon atoms, an alkenylene group of 3 to 18 carbon atoms, or a phenylene or xylylene group which may optionally be substituted by an alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, or an alkoxycarbonyl group of 2 to 6 carbon atoms; Y1 represents -NHCO-, -CONH-, -NHCS-, -COO-, -COS-, -O- or -S-; Y2 represents -CONH-, -NHCO-, -CSNH-, -OOC-, -SOC-, -O- or -S-; and X represents anions.
- The antibacterial and antifungal resin compositions will be more specifically described hereinbelow.
- As used herein, the term "alkyl group" denotes a straight-chain or branched alkyl group, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl and octadecyl, etc. From the viewpoint of antibacterial power, the alkyl groups represented by R1 are preferably ones having 8 or more carbon atoms.
- The term "alkenyl group" denotes a straight-chain or branched alkenyl group, and examples thereof include allyl, methallyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl and octadecenyl, etc.
- The term "alkoxy group" denotes an alkyloxy group in which the alkyl moiety has the above-described meaning, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy.
- The term "alkylene group" preferably denotes a group of the formula -(-CH2-)n-. In this formula, n is preferably in the range of 2 to 18 and more preferably 3 to 8.
- The term "alkenylene group" comprehends, for example, -CH=CH-, -CH=CH-CH2- and -CH2-CH=CH-CH2-.
- The term "alkoxycarbonyl group" denotes an alkyloxycarbonyl group in which the alkyl moiety has the above-described meaning, and examples thereof include methoxycarbonyl and ethoxycarbonyl.
- The term "halogen atom" comprehends fluorine, chlorine, bromine and iodine.
- The term "anion" comprehends inorganic anions such as halogen ions (e.g., Cl-, Br- and I-) and nitrate ion (NO3 -); and organic acid anions such as acetate ion (CH3COO-) and propionate ion (C2H5COO-).
- Among the compounds represented by the above formula (I), a preferred group of compounds are those of formula (I) in which the two R1 may be the same or different, and each represent an alkyl group of 8 to 18 carbon atoms; the two R2 may be the same or different, and each represent a hydrogen atom or a chlorine atom; R3 represents an alkylene group of 3 to 8 carbon atoms, a phenylene group or a xylylene group; Y1 represents -NHCO-, -CONH-, -COO- or -S-; Y2 represents -CONH-, -NHCO-, -OOC- or -S-; and X represents a halogen ion or an acetate ion.
- Specific examples of the compounds of the above formula (I) used as antibacterials in the present invention are as follows:
- N,N'-Hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) ("Dimer 38"; manufactured by INUI CORPORATION),
- N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium acetate) ("Dimer 38A"; manufactured by INUI CORPORATION),
- 4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide) ("Dimer 136"; manufactured by INUI CORPORATION),
- 4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium acetate) ("Dimer 136A"; manufactured by INUI CORPORATION),
- 1,4-tetramethylenebis(4-carbamoyl-1-hexadecylpyridinium bromide),
- 1,6-hexamethylenebis(3-carbamoyl-1-dodecylpyridinium bromide),
- 1,6-octamethylenebis(3-carbamoyl-1-tetradecylpyridinium bromide),
- 3,3'-(1,3-trimethylenedicarbonyldiamino)bis(1-dodecylpyridinium bromide),
- 4,4'-(p-xylyldithio)bis(1-octylpyridinium iodide),
- 3,3'-(m-xylyldithio)bis(1-tetradecylpyridinium bromide),
- N,N'-(p-phenylene)bis(4-carbamoyl-1-octylpyridinium bromide),
- N,N'-(m-phenylene)bis(3-carbamoyl-1-dodecylpyridinium bromide).
- 4,4'-(p-phthalamido)bis(1-octylpyridinium bromide),
- 3,3'-(m-phthalamido)bis(1-octadecylpyridinium iodide),
- 4,4'-(1,8-octamethylenedioxy)bis(1-dodecylpyridinium bromide),
- 3,3'-(1,6-hexamethylenedioxy)bis(1-hexadecylpyridinium bromide),
- 4,4'-(1,6-hexamethylenedioxydicarbonyl)bis(1-octylpyridinium bromide),
- 3,3'-(1,6-tetramethylenedioxydicarbonyl)bis(1-dodecylpyridinium bromide),
- 4,4'-(1,4-tetramethylenedicarbonyldioxy)bis(1-octylpyridinium bromide).
- 3,3'-(p-phthaloyldioxy)bis(1-decylpyridinium chloride),
- 4,4'-(1,8-octamethylenedicarbonyldithioxy)bis(1-octadecylpyridinium bromide) and
- 3,3'-(m-phthaloyldithioxy)bis(1-decylpyridinium iodide).
-
- The compounds of the above formula (I) are disclosed, for example, in the publications of Japanese Patent Laid-Open Nos. 110692/'97, 95773/'98 and 287566/'98 and the specifications of Japanese Patent Application Nos. 282071/'98 and 321347/'98, all of which were filed in the name of the present applicant, or may be prepared according to the processes described in these publications or specifications.
- On the other hand. no particular limitation is placed on the type of the polymeric resin in which the antibacterial compound of the above formula (I) is incorporated according to the present invention, and any desired polymeric resin may be freely chosen according to the intended use of the resin composition of the present invention, and the like. Concrete examples of usable resins include vinyl chloride polymers. urethane polymers. acrylate polymers, olefin polymers, ethylene polymer, propylene polymer, polyamides, ethylene-vinyl acetate copolymers, vinylidene chloride polymer, styrene polymers, ester polymers, nylons, cellulose derivatives, polycarbonates, fluorinated resins, silicone resins, vinyl alcohol polymers, vinyl ester polymers, compounds and natural rubber. These resins may be used alone or as a blend of two or more.
- The antibacterial and antifungal resin compositions used in the present invention may be prepared by dispersing an antibacterial compound of the above formula (I) in a polymeric resin as described above. More specifically, the resin compositions may be obtained, for example, by adding the compound of formula (I) in the polymeric resin and melt-kneading this mixture, by adding the compound of formula (I) or a solution thereof to a solution of the polymeric resin and agitating this mixture, or by polymerizing a monomer and monomers with the compound of formula (I) or a solution thereof. Alternatively, the compound of formula (I) may be chemically bonded to the polymeric resin.
- The amount of the compound of formula (I) incorporated in the polymeric resin is not strictly limited, but may vary according to the type of the resin used, the type of the compound of formula (I) used, the use of the resulting resin composition, and the like. However, the amount is generally in the range of 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 2 part by weight, per 100 parts by weight of the polymeric resin.
- If necessary, plasticizers, fillers, colorants (i.e., dyes and pigments), ultraviolet-radiation absorbers and other additives may optionally be incorporated in the resin compositions of the present invention.
- The resin compositions used in the present invention may be processed into various forms according to their intended use and the like. For example, according to per se known resin processing techniques such as extrusion molding, injection molding, solution casting and spinning, the resin compositions of the present invention may be formed into films, sheets, plates, fibers or three-dimensional articles, and may be used, for concrete example, as interior decorative materials (e.g., wallpaper), as flooring materials (e.g., tiles), and in home electrical appliances (e.g., refrigerators, washing machines and dryers).
- Moreover, the resin compositions used in the present invention may also be formed into antibacterial paints by using them as vehicles. This can be done, for example, by dissolving or dispersing the resin composition in a paint solvent and adding suitable paint additives (e.g.; pigments and crosslinking agents) to the resulting solution or dispersion.
- Furthermore, in order to impart antibacterial and antifungal processing to fibrous or textile products and paper products, the resin compositions of the present invention may be applied to . fiber products and paper products in the form of organic solvents or aqueous emulsions. The applications include, for example, padding, dipping, spraying, printing, coating, gravure coating and foam laminating. The polymeric resins suitable for use in such treatment of fiber products and paper products include, for example, starch, carboxymethylcellulose, urethane resins, acrylate resins, epoxy resins, vinyl chloride resins, vinyl acetate resins, fluorinated resins, silicone resins, polyamide resins, polyester resins, glyoxal resin, polyvinylidene fluoride resins, styrene resins, butadiene resins, acrylonitrile-butadiene resins, acrylate resins, ethylene-vinyl acetate resins, acrylate-ethylene-vinyl acetate resins and ethylene-vinyl chloride resins.
- No particular limitation is placed on the types of the fiber products and paper products which can be treated with the resin compositions of the present invention to impart antibacterial and antifungal processing thereto. They include, for example, various kinds of products formed from synthetic fibers such as polyester fibers, polyamide fibers, acrylic fibers, polyolefin fibers and polyvinyl chloride fibers; semisynthetic fibers such as acetates; regenerated fibers such as rayon; natural fibers such as cotton, flax, wool, silk and pulp; and composite materials obtained from these fibers by mix spinning, mixed weaving, combined twisting, combined weaving, combined knitting or fiber blending. More specifically, they include fibers such as filaments and staple, threads such as filament yarn and spun yarn; textile materials such as woven fabrics, knitted fabrics and nonwoven fabrics; paper-like materials formed of fibers; and fiber products and paper products made of these materials.
- The fiber and paper products treated with said resin compositions include, for example, linen products for use in hospitals, sanitary products, bedclothes, socks, supporters, carpets, toiletry goods, kitchen utensils, toys, filters for electrical appliances, wet tissue, helmets and wallpaper, etc.
- According to a specific embodiment of the present invention, a highly water-absorbing resin may be used as the starting resin. This makes it possible to provide a water-absorbing resin composition which has excellent deodorant properties and can hence be used in sanitary products including, in particular, disposable diapers, and urine disposal articles for pets.
- As the highly water-absorbing resin included in this water-absorbing resin composition, there may be used any of the highly water-absorbing resins commonly used in disposable diapers and sanitary products (e.g., sanitary napkins). Examples thereof include starch-based water-absorbing resins such as soluble starch-acrylonitrile graft copolymer and starch-acrylic acid graft copolymer; cellulose-based water-absorbing resins such as crosslinked graft cellulose and crosslinked carboxymethylcellulose; and synthetic polymer-based water-absorbing resins such as partially crosslinked polyoxyethylene, partially crosslinked acrylate or methacrylate polymers, partially crosslinked acrylate or methacrylate copolymers, and vinyl alcohol-acrylate copolymer. It is generally preferable that these resins have the ability to absorb several hundred to several thousand times as much water as their own weight. The resins may be used alone or in combination of two or more.
- An antibacterial compound of the above formula (I) may be incorporated in such a highly water-absorbing resin according to any of the per se known methods. This may be done, for example, (1) by allowing a powder of the highly water-absorbing resin to absorb an aqueous solution containing an appropriate amount of the compound of formula (I), followed drying; (2) by adding an appropriate amount of the compound of formula (I), in the form of a powder or a solution, to the highly water-absorbing resin at any stage of the preparation of the resin; or (3) by mixing a powder of the highly water-absorbing resin with an appropriate amount of the compound of formula (I) in powder form. However, the above-described methods (1) and (2) are preferred for the purpose of highly dispersing the compound of formula (I).
- The water-absorbing resin composition prepared in the above-described manner may be processed into various forms. No particular limitation is placed on such forms. For example, the water-absorbing resin composition may be formed into powders, granules, sheets or fibers according to the intended use of the final product, and the like. Moreover, it may be formed into water-absorbing fibers of two-layer structure in which an acrylic fiber is incorporated as the core (e.g., "Lanseal F" manufactured by Toyobo Co., Ltd.).
- The amount of the antibacterial compound of formula (I) incorporated in the highly water-absorbing resin is not strictly limited, but may vary according to the type of the antibacterial compound used, and the like. However, the antibacterial compound of formula (I) is generally used in an amount of 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 2 parts by weight, per 100 parts by weight of the resin.
- When the highly water-absorbing resin having the antibacterial compound of formula (I) incorporated therein as described above is used as a water-absorbing resin for sanitary products and, in particular, disposable diapers, it becomes possible to provide hygienic disposable diapers which can effectively prevent the generation of an offensive odor arising from urinary excretion. Specifically, in disposable diapers consisting of a water-pervious facing sheet, a water-impervious backing sheet, and a water-absorbing layer interposed between these sheets, the highly water-absorbing resin conventionally used in the water-absorbing layer may be replaced by the water-absorbing resin composition of the present invention. The disposable diapers thus obtained can inhibit the growth of bacteria decomposing urea and other compounds present in urine to produce ammonia, methylamine, etc., and thereby prevent the generation of an offensive odor due to the decomposition of urea and other compounds. Moreover, they can also inhibit the growth of various microorganisms such as Escherichia coli and Candida species, and can hence be expected to improve unhygienic conditions attributable to such various microorganisms.
- In addition, when the highly water-absorbing resin having the antibacterial compound of formula (I) is used in urine disposal articles for pets, it can be expected that they have an excellent deodorant effect.
- It frequently happens that pets are kept at home. Especially when pets are kept indoors. the keeper is often troubled with the disposal of excretion therefrom and an offensive odor emitted thereby. Litter for a cat box (cat sand) is commonly used as a urine disposal article for pets. Generally, litter comprising ordinary sand is used to absorb and retain excretion from pets. After a while, the litter is washed, dried and reused, but this has the disadvantage of requiring much labor. Moreover, if the interval between replacements is lengthened, an unhygienic condition is developed owing to the emission of an offensive odor and the generation of various microorganisms. In order to solve these problems, litter comprising a highly water-absorbing resin and, moreover, such litter having added thereto antibacterials and a deodorant have recently come into the market. In the present circumstance, however, they are not satisfactorily effective in preventing the generation of an offensive odor. Although some patience or habituation may make the keeper insensitive to the odor of pets because they are practically members of the family, occasional visitors tend to suffer from an unpleasant odor.
- As demonstrated in the examples which will be given later, the deodorant water-absorbing resin compositions of the present invention can more effectively prevent the generation of an offensive odor due to the decomposition of urine, and the growth of various microorganisms, than other antibacterials. Accordingly, the deodorant water-absorbing resin compositions used in the present invention can contribute greatly to the prevention of an offensive odor arising from pets, the maintenance of a hygienic environment, and a decrease in the freq offensive odor uency of exchange of urine disposal articles for pets.
- The present invention is further illustrated by the following examples. However, these examples are not to be construed tc limit the scope of the invention.
- Antibacterial urethanes were obtained by adding 1 phr of N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide) (hereinafter referred to as "Dimer 38"), 4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide) (hereinafter referred to as "Dimer 136) or inorganic antibacterials containing silver to an ether type urethane and an ester type urethane. The antibacterial urethanes thus obtained were subjected to antibacterial tests according to a film covering method. Concretely, each specimen (5 cm x 5 cm) was placed in a sterile petri dish, and the test surface was inoculated with 0.5 ml of a cell suspension and was covered with a sterile polyethylene film. The petri dish was covered and allowed to stand at 37°C for 24 hours. Thereafter, using SCDLP medium (9.5 ml), the bacterial cells attached to the specimen and the coating film were thoroughly washed out into the another sterile petri dish. The viable cell number present in 1 ml of the washings was counted according to the agar dilution method. Three specimens were tested for each sample, and the viable cell count was calculated as the average of the three specimens. For this purpose, two strains of bacteria, Staphylococcus aureus IFO 12732 and Escherichia coli K12 W3110, were used. The results thus obtained are shown in Table 1.
- It can be seen from the results shown above in Table 1 that the sheets containing Dimer 38 or Dimer 136 have excellent antibacterial efficiency.
- Antifungal vinyl chloride polymer sheets were formed from polyvinyl chloride having 0.5% of Dimer 38, Dimer 136 or inorganic antibacterials containing zinc. Fungus resistance of the antifungal sheets were assessed by the modified method of JIS Z 2911 (Japanese Industrial Standards Committee, 1992). Concretely, a specimen (4 cm x 4 cm) of each sheet was placed in a petri dish containing a mineral nutrient agar, and 0.5 ml of the mixed spore suspension was uniformly inoculated on the agar and the specimen. The petri dish was covered, incubated at 28°C for 9 weeks, and observed for the growth of fungi at intervals of one week. For this purpose, the blend of spore suspension of four strains of fungi, Aspergillus niger IFO 6341, Penicillium funiculosum IFO 6345, Chaetomium globosum IFO 6347 and Aureobasidium pullulans IFO 6353, were used. The results thus obtained are shown in Table 2. The symbols (○, Δ and X) given in Table 2 have the following meanings.
- ○ =
- No growth of fungi was recognized on the sheet inoculated with the blend of spore suspension.
- Δ =
- The growth of fungi was recognized in 1/3 or less of the total area of the sheet inoculated with the blend of spore suspension.
- X =
- The growth of fungi was recognized in more than 1/3 of the total area of the sheet inoculated with the blend of spore suspension.
- It can be seen from the results shown in Table 2 that the sheets with Dimer 38 or Dimer 136 exhibit stronger antifungal efficiency than the commercially available sheet containing inorganic antibacterials containing zinc. Especially in the case of the Dimer 136-containing antifungal sheet, no growth of fungi was observed even after 9 weeks of culturing, indicating that it has excellent antifungal efficiency.
- Water-absorbing resins containing antibacterials (herein referred to as "antibacterial SAPs") were prepared by allowing 1 g of a highly water-absorbing resin powder ("AQUAPEARL ZS45"; manufactured by Mitsubishi Chemical Co., Ltd.) to absorb 10 g of an aqueous solution of antibacterials having each concentration of 500, 100 or 20 ppm, and then drying the resin at 130°C. The antibacterials comprised (Dimer 38). N,N'-hexamethylene-bis(4-carbamoyl-1-decylpyridinium acetate) (hereinafter referred to as Dimer 38A) or benzalkonium chloride. One gram of each of the antibacterial SAPs was placed in a sterile petri dish, inoculated with 10 ml of the cell suspension in stationary phase, and was incubated at 37°C for 24 hours. Thereafter, 1 g of the resin solution, which was in the form of a gel, was taken and added to 9 ml of sterilized physiological saline, followed by vigorous agitation. Then, the viable cell count present in the supernatant was observed. For this purpose, two strains of bacteria, MRSA (Staphylococcus aureus JC1) and Escherichia coli K12 W3110, were used. The results thus obtained are shown in Table 3.
- It can be seen from the results shown above in Table 3 that the SAPs containing Dimer 38 or Dimer 38A have excellent antibacterial efficiency.
- Antibacterial SAPs containing Dimer 38, Dimer 38A or benzalkonium chloride were prepared in the same method as in Example 3. One gram of each of the antibacterial SAPs thus obtained was placed in a test tube, to which 10 ml of human urine and 1 ml of the cell suspension (about 106 cells/ml) of Proteus mirabilis IFO 3849 were added. The test tube was incubated at 37°C. After 6 and 24 hours, the concentration of ammonia in the test tube was measured with a smell sensor (Portable Smell Sensor XP-329; manufactured by Shin Cosmos Electric Co., Ltd.). The results are shown in Table 4.
- It can be seen from the results shown in Table 4 that the SAPs containing Dimer 38 or Dimer 38A caused no ammonia to be detected and hence have excellent deodorant efficiency.
- The minimum inhibitory concentrations (MICs), namely the bacteriostasis powers, of Dimer 38 and Dimer 136 were determined and compared with that of benzalkonium chloride. Their minimum inhibitory concentrations (MICs) of antimicrobials were measured by the broth dilution method. Concretely, using nutrient broth, the cell concentration in stationary phase was adjusted to 106 cells/ml, and aliquots thereof were mixed with serially diluted solutions of each antibacterials. These mixtures were incubated at 37°C for 24 hours and the MICs were determined by visual inspection. In these tests, 8 strains of gram-negative bacteria and 4 strains of gram-positive bacteria were used. The results are shown in Table 5.
Bacteria MIC (ppm) Dimer 38 Dimer 136 Benzalkonium chloride Pseudomonas aeruginosa ATCC 27583 5 5 25 Pseudomonas aeruginosa ATCC 10145 5 5 25 Klebsiella pneumoniae ATCC 4352 2.5 2.5 5 Klebsiella pneumoniae ATCC 13883 5 1 50 Proteus rettgeri NIH 96 5 2.5 25 Proteus mirabilis IFO 3849 25 10 100 Escherichia coli K12 OUT 8401 1 1 5 Escherichia coli K12 W3110 2.5 2.5 10 Bacillus subtilis ATCC 6633 0.5 0.5 2.5 Bacillus cereus IFO 3001 1 1 2.5 Staphylococcus aureus IFO 12732 1 <0.5 2.5 Staphylococcus aureus JC1 (MRSA) 0.5 0.5 10 - It is evident from the results shown in Table 5 that Dimer 38 and Dimer 136 exhibit equally strong bacteriostatic efficiency against all of the 8 strains of gram-negative bacteria including Escherichia coli and the 4 strains of gram-positive bacteria including MRSA, and hence have wide bacteriostatic spectra over that of benzalkonium chloride. When attention is paid to the bacteriostasis against Proteus mirabilis IFO 3849 that is a bacterium producing an enzyme (urease) capable of degrading urea and other compounds to ammonia, methylamine, etc., the bacteriostasis of Dimer 38 is four times and that of Dimer 136 is ten times stronger, as compared with that of benzalkonium chloride.
- The minimum inhibitory concentrations (MICs), namely the antifungal efficiency, of Dimer 38 and Dimer 136 were determined and compared with that of 2-(4-thiazolyl)benzimidazole (hereinafter referred to as "TBZ"). (MICs) were measured by the broth dilution method. Concretely, using sterilized water containing a humectant, spore suspensions were prepared from preincubated fungi, and aliquots thereof were mixed with serially diluted solutions of each antibacterial or antifungal agent. These mixtures were incubated at 27°C for 1 week and the MICs were determined by visual inspection. In these antifungal tests, 10 strains of fungi were used. The results thus obtained are shown in Table 6.
Fungi MIC (ppm) Dimer 38 Dimer 136 TBZ Aspergillus niger TSY 0013 10 10 25 Aspergillus niger IFO 6341 10 10 25 Aspergillus terreus IFO 6346 2.5 10 10 Aureohasidium pullulans IFO 6353 0.5 2.5 0.5 Chaetomium globosum IFO 6347 1 2.5 1 Cladosporium cladosporioides IFO 6348 2.5 2.5 1 Gliocladium virens IFO 6355 0.5 1 1 Trichoderma viride IFO 30498 5 5 25 Penicillium funiculosum IFO 6345 2.5 2.5 1 Rhizopus nigricans SN 32 10 10 50 - It is evident from the results shown in Table 6 that, as compared with TBZ, both of Dimer 38 and Dimer 136 exhibit equal or stronger antifungal efficiency against all of the 10 strains of fungi, and hence have wide antifungal spectra.
- As described above, the antibacterial and antifungal resin compositions used in the present invention each comprise a polymeric resin containing an antibacterial bis-pyridinum compound which not only inhibits the growth of bacteria and shows a wide antibacterial spectrum than usual Quaternary ammonium salt compounds, but also has an antifungal effect on fungi. Consequently, they can be used in a wide range of applications requiring antibacterial and antifungal properties from the viewpoint of health and hygiene, and can be expected to improve unhygienic conditions attributable to bacteria and fungi.
Week | Fungus resistance | |||
Dimer 38 | Dimer 136 | Inorganic antibacterials containing zinc | Control | |
1 | ○ | ○ | ○ | Δ |
2 | ○ | ○ | ○ | X |
3 | ○ | ○ | ○ | X |
4 | ○ | ○ | Δ | X |
5 | X | ○ | X | X |
6 | X | ○ | X | X |
7 | X | ○ | X | X |
8 | X | ○ | X | X |
9 | X | ○ | X | X |
Claims (4)
- A disposable diaper characterized by using, as a water-absorbing material, a deodorant water-absorbing resin composition comprising a highly water-absorbing resin and an antibacterial bis-pyridinium compound of the general formula: wherein the two R1 may be the same or different, and each represent an alkyl group of 1 to 18 carbon atoms or an alkenyl group of 3 to 18 carbon atoms; the two R2 may be the same or different, and each represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkyl group of 1 to 6 carbon atoms, or an alkoxy group of 1 to 3 carbon atoms; R3 represents an alkylene group of 2 to 18 carbon atoms, an alkenylene group of 3 to 18 carbon atoms, or a phenylene or xylylene group which may optionally be substituted by an alkyl group of 1 to 18 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, or an alkoxycarbonyl group of 2 to 6 carbon atoms; Y1 represents -NHCO-, -CONH-, -NHCS-, -COO-, -COS-, -O- or -S-; Y2 represents -CONH-, -NHCO-, -CSNH-, -OOC-, -SOC-, -O- or -S-; and X represents an anion.
- A urine disposal article for pets characterized by comprising a deodorant water-absorbing resin composition comprising a highly water-absorbing resin and an antibacterial bis-pyridinium compound of the general formula (I) as defined in claim 1.
- The product of claim 1 or 2 wherein the compound of formula (I) is selected from the group consisting ofN,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide),N,N'-hexamethylenebis(4-carbamoyl-1-decylpyridinium acetate),4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium bromide),4,4'-(tetramethylenedicarbonyldiamino)bis(1-decylpyridinium acetate),N,N'-(1,4-tetramethylene)bis(4-carbamoyl-1-hexadecyl-pyridinium bromide),N,N'-(1,6-hexamethylene)bis(3-carbamoyl-1-dodecylpyridinium bromide),N,N'-(1,6-octamethylene)bis(3-carbamoyl-1-tetradecylpyridinium bromide),3,3'-(1,3-trimethylenedicarbonyldiamino)bis(1-dodecylpyridinium bromide),4,4'-(p-xylyldithio)bis(1-octylpyridinium iodide),3,3'-(m-xylyldithio)bis(1-tetradecylpyridinium bromide),N,N'-(p-phenylene)bis(4-carbamoyl-1-octylpyridinium bromide),N,N'-(m-phenylene)bis(3-carbamoyl-1-dodecylpyridinium bromide),4,4'-(p-phthalamido)bis(1-octylpyridinium bromide),3,3'-(m-phthalamido)bis(1-octadecylpyridinium iodide),4,4'-(1,8-octamethylenedioxy)bis(1-dodecylpyridinium bromide),3,3'-(1,6-hexamethylenedioxy)bis(1-hexadecylpyridinium bromide),4,4'-(1,6-hexamethylenedioxydicarbonyl)bis(1-octylpyridinium bromide),3,3'-(1,6-tetramethylenedioxydicarbonyl)bis(1-dodecylpyridinium bromide),4,4'-(1,4-tetramethylenedicarbonyldioxy)bis(1-octylpyridinium bromide),3,3'-(p-phthaloyldioxy)bis(1-decylpyridinium chloride),4,4'-(1,8-octamethylenedicarbonyldithioxy)bis(1-octadecylpyridinium bromide) and3,3'-(m-phthaloyldithioxy)bis(1-decylpyridinium iodide).
- The product of claim 1 or 2 wherein the resin composition contains the compound of formula (I) in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the resin.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31313998 | 1998-11-04 | ||
JP10313139A JP2000136315A (en) | 1998-11-04 | 1998-11-04 | Deodorant water-absorbing resin composition |
JP37374198 | 1998-12-28 | ||
JP10373741A JP2000198879A (en) | 1998-12-28 | 1998-12-28 | Antibacterial/antifungal resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0998851A1 EP0998851A1 (en) | 2000-05-10 |
EP0998851B1 true EP0998851B1 (en) | 2004-01-28 |
Family
ID=26567460
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99120991A Expired - Lifetime EP0998851B1 (en) | 1998-11-04 | 1999-11-04 | Antibacterial and antifungal resin composition |
Country Status (3)
Country | Link |
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US (1) | US6251381B1 (en) |
EP (1) | EP0998851B1 (en) |
DE (1) | DE69914436D1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0204087D0 (en) * | 2002-02-21 | 2002-04-10 | Legislator 1563 Ltd | Di-ester derivatives as short acting neuromuscular blockers |
JP2004345953A (en) * | 2003-01-16 | 2004-12-09 | Hiroki Koma | New quaternary ammonium salt compound having anti-bacterial activity and method for producing the same |
US8138106B2 (en) | 2005-09-30 | 2012-03-20 | Rayonier Trs Holdings Inc. | Cellulosic fibers with odor control characteristics |
JP4094046B2 (en) * | 2006-09-25 | 2008-06-04 | トヨタ自動車株式会社 | Deodorized fabric and method for deodorizing fabric |
JP4925801B2 (en) * | 2006-11-30 | 2012-05-09 | 日本エンバイロケミカルズ株式会社 | Microbial control agent and stabilization method |
WO2008150460A1 (en) * | 2007-05-30 | 2008-12-11 | Research Foundation Of The City University Of New York | Embedding antibiotic compounds in solid polymers |
US20140377467A1 (en) * | 2010-02-15 | 2014-12-25 | Philadelphia University | Textiles having antimicrobial properties and methods for producing the same |
US20140273690A1 (en) * | 2013-03-15 | 2014-09-18 | Philadelphia University | Antimicrobial textiles and methods for production of the same |
WO2016172436A1 (en) | 2015-04-23 | 2016-10-27 | Temple University-Of The Commonwealth System Of Higher Education | Polycationic amphiphiles and polymers thereof as antimicrobial agents and methods using same |
WO2018081347A1 (en) * | 2016-10-26 | 2018-05-03 | Temple University-Of The Commonwealth System Of Higher Education | Polycationic amphiphiles as antimicrobial agents and methods using same |
CN113736200A (en) * | 2021-10-15 | 2021-12-03 | 威高集团有限公司 | Antibacterial super absorbent resin composite material and preparation method thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1339764A (en) | 1971-03-29 | 1973-12-05 | Ici Ltd | Pyridine derivatives |
DE4217884A1 (en) | 1992-05-29 | 1993-12-02 | Henkel Kgaa | Highly effective antimicrobial biocide combinations |
JPH09110692A (en) | 1995-10-19 | 1997-04-28 | Inui Kk | Bis quaternary ammonium salt compound having antimicrobial activity and its production |
JPH1095773A (en) | 1996-09-19 | 1998-04-14 | Inui Kk | Bisquaternary ammonium salt compound having antimicrobial activity and its production |
JPH10287566A (en) | 1997-04-08 | 1998-10-27 | Inui Kk | Bis quaternary ammonium salt compound having antimicrobial activity and its production |
-
1999
- 1999-11-01 US US09/431,051 patent/US6251381B1/en not_active Expired - Fee Related
- 1999-11-04 DE DE69914436T patent/DE69914436D1/en not_active Expired - Lifetime
- 1999-11-04 EP EP99120991A patent/EP0998851B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US6251381B1 (en) | 2001-06-26 |
DE69914436D1 (en) | 2004-03-04 |
EP0998851A1 (en) | 2000-05-10 |
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